Resonance-Assisted Hydrogen Bonding Mediated Synergy between Energy and Safety in Energetic Materials: Experimental Inspiration and Mechanism Research

Resonance-assisted hydrogen bonding (RAHB) plays a critical role in the design of energetic materials, yet its mechanistic influence on balancing energy and safety remains unclear. This work synthesized compound 1,3,5-triamino-2,4-dinitrobenzene (TADNB) through experiments and studied its properties, discovering the unique coordination of RAHB between the energetic properties and safety. Then, we systematically investigate the regulatory effects of RAHB on the structure and properties of nitrobenzene-based explosives through theoretical calculations. The results reveal that RAHB promotes the transfer of delocalized electrons from the benzene ring to quasi-cyclic structures, enhancing molecular planarity, C-NO2 bond energy, and nitro group charge density, while optimizing intra- and intermolecular interactions. As the number of RAHBs increases, the crystal packing transitions from mixed stacking to more stable face-to-face stacking, significantly strengthening the intermolecular interaction. These findings demonstrate that RAHB enables dual optimization of energy and safety in energetic materials by synergistically modulating the electronic structure, molecular packing, and bond characteristics, offering a novel strategy for designing high-energy, low-sensitivity materials.